New vat dyestuffs of the benzanthrone series and process of making same



Patented Aug. 18, 1931 are rares WERNER ZERWECK AND ERNST HONOLD, OF FRANKFORT-ON-TI-IE-IVIAIN-FECHENHEIM,

GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y. A I

CORPORATION OF DELAWARE.

NEW VAT DYESTUFFS OF THE BENZANTI-IRONE SERIES AND PROCESS OF MAKING SAME No Drawing. Application filed. February 6, 1929, Serial No. 338,624, and in Germany February 10,1928.

Our present invention relates to new vat dyestufi's and to a process of making them, more particularly it relates to new vat dyestuffs of the benzanthroneseries obtainable by acting with an acid condensing agent on an benZanthronyl-amino anthraquinone containing at least one aroylamino group in the anthraquinone residue and corresponding probably to the general formula:

ride, chlorosulfonic and sulfuric acid may be named. The course of the reaction can not 5; be given with certainty; it may be assumed that the condensation takes place between the benzanthrone and the anthraquinone res idues and that products are formed which contain a new carbazol-like ring, while apgdiparently the aroylaminogroup is not attacked. w I

The new products are when dry dark powders soluble in concentrated sulfuric acid with a bluish to violet color, they forn witli 'I an alkaline hydrosulfite solution brownish to bluish to violet vats from which the vegetable fiber is dyed brownish to greenish to bluish shades of an excellent fastness.

When using sulfuric or chlorosulfonic acid 'l as a condensing agent in some casessimultaneously a sulfonic acid group can be introduced into the molecule of the condensation products, a fact which favors their solubility in the vat without afiecting their fastness properties.

In order to further illustrate our invention thefollowing examples are given, the parts being by Weight and all temperatures in ceutigrade degrees, but it is understood, 5

that our invention is not limited to the particular products or reacting conditions men- .7

tioned therein. I

Example 1 benz oyl-amino-anthraquinone- (soluble concentrated sulfuric acid with a browncolor, obtainable by condensing l-amin0-5-i benzoyl-amino-anthraquinone for some time at this temperature. Then it is poured on water and after boiling up the acidified mass inorder to dissolve the alu- V minium compounds the separated dyestuif is filtered 01f. It dissolves in concentrated sulfuric acid with'a blue color,-it is dfiicultly soluble in an alkaline hydrosulfite solution with a dark brown color and dyes cotton from this vat bright yellowish brown tints of i an excellent fastness.

The ring closure occurring probably by the w reaction may be illustrated by the dotted line in the following formula:

with bz-l- Y bromobenzanthrone) are introduced at about 130440 into a mixture of about 250 parts of anhydrous aluminium chloride and 50 parts of sodium chloride and the mass is kept 5 in 800 parts of sulfuric acid inonohydrate is stirred at 2030 for some hours, until the previously dark brown solution has turned to a pure blue coloration. Then the mass is poured on ice and the separated dyestufi' is filtered off. It corresponds in its properties to the dyestuff obtainable according to Example 1, but it is superior as to its solubility in the vat. Apparently the structure of the condensation product is identical with that given in Example 1, but it contains a sulfonic acid group.

When starting from the condensation product of l-amino-5benzoyl-aminoanthraquinone with 6-bz-l-dibrombenzanthrone, a dyestuif is obtained which is soluble in concentrated sulfuric acid with a greenish blue color. It dyes cotton yellowish brown shades.

' Ewample 5 20 parts of .2-benzanthronyl-l-amino-tbenzoyl-aminoanthrmgiinone (obtainable by condensing 2-chloroenzanthrone with '1- amino-4-benzoylaminoanthraquinone) a r e dissolved while stirring at about 2025 in "160 parts of chlorosulfonic acid. The solutionisstirred for some hours at the same temperature and then it is allowed to run into about 200 parts of sulfuric acid of about 62 per cent strength. When the evolution of hydrochloric :acid has ceased the separated reddish violet sulfate of the condensation product is filtered off and converted into the dyest-uff by treatment with water. The dyest-uiff represents when dry a dark green pow- "der difficultly soluble in organic solvents of a higher boiling point such as nitrobenzene with a yellowish green color, in sulfuric acid of about 82 per centstrength with a reddish blue .color. It forms a violet vat and dyes cotton therefrom strong yellowish green shades of an excellent fastness.

In an analogous manner as shown in Example 1 the ring closure probably involved ,by the reaction may be illustrated by the dotted line in the following formula:

The reaction may be carried out likewise by using other acid condensing agents such as sulfurlc acid monohydrate or fuming sulfurlc acid.

Example 4 30 parts of (6-benzanthronyl)-1-amino-4- benzoylaminoanthraquinone (obtainable by condensing l-amino-4-benzoylaminoanthraquinone with 6-chlorobenzantln'one) are dissolved in Q00 parts of chlorosulfonic acid and the solution is kept at about for some time. The dyestufi is isolated in the usual manner. Whereas the starting material dissolves in sulfuric acid with a brown color the dyestuff dissolves with a bluish green color. It

forms an orange brown vat and dyes cotton grey brown shades. According'to the statements made above we ascribe to it the follow ing formula:

When starting from the isomeric condensation product obtainable by condensing 6- chlorobenzanthrone wiih 1-amino-5-benzoylamino-anthraquinone (dissolving with a brown color in concentrated sulfuric acid) and carrying out the process correspondingly a dyestuif is obtained, which dissolves in sulfuric acid with a greenish blue color and dyes cotton from a brown vat yellowish brown shades.

Example 5 20 parts of the condensation product obtainable by condensing one molecular proportion of 2.6-dichloro-benzanthrone with fastness are obtained. WVe ascribe to the dyestufl? the following probable formula:

O (NH-CO-aryl) wherein the benzanthrone as well as the anthraquinone and the aryl residue may contain further substituents.

2. A process which comprises acting with an acid condensing agent of the group con sisting of chloro-sulfonic acid, sulfuric acid and aluminium chloride on a benzanthronylamino-anthraquinone compound containing at least one aryl-amino-group in the anthraquinone residue and corresponding probably to the general formula:

wherein the benzanthrone as well as the anthraquinone and the aryl residue may contain further substituents.

3. A process which comprises acting with an acid condensing agent of the group consisting of sulfuric and chlorosulfonic acid on a benzanthronyl-amino-anthroquinone compound containing' at least one aroyl-aminogroup in the anthraquinone residue and corresponding probablyto the'general formula:

wherein the benzanthrone as well as the'anthraquinone and the aryl residue may contain further substituents. v

4. As new compounds condensation products corresponding probably to the general formula:

wherein the benzanthrone as well as the anthraquinone and the benzene residue may contain further substituents which compounds are when dry dark powders soluble in concentrated sulfuric acid with a bluish to violet color, which form brownish to bluish to violet vats with an alkaline hydrosulfite solution and dye the vegetable fiber therefrom brownish to greenish to bluish shades of an excellent fastness.

5. As new compounds condensation prod ucts corresponding probably to the general formula:

wherein the benzanthrone as well as the anthraquinone and the benzene residue may contain further substituents at least one sulfonic acid group being present in the molecule, which compounds are when dry dark powders soluble in concentrated sulfuric acid with a bluish to violet color, which form brownish to bluish to violet vats with an alkaline hydrosulfite solution and dye the vegetable fiber therefrom brownish to greenis'h' to-bluish shades of anrex'cellent fas'tness. V 6. As a: new compound the dyestuff of the probable formula: t

soluble in concentrated sulfuric acid with a blue color, forming a dark brown vat and dyeing cotton therefrom bright yellowish brown tints of an excellent fastness.

In testimony whereof, We ailix our signatures. 

